CN107185572A

CN107185572A - Fischer-tropsch synthetic catalyst comprising nitride carrier and its preparation method and application

Info

Publication number: CN107185572A
Application number: CN201710320760.4A
Authority: CN
Inventors: 张成华; 王虎林; 王宪周; 相宏伟; 杨勇; 李永旺
Original assignee: Zhongke Synthetic Oil Technology Co Ltd
Current assignee: Synfuels China Technology Co Ltd; Zhongke Synthetic Oil Technology Co Ltd
Priority date: 2017-05-09
Filing date: 2017-05-09
Publication date: 2017-09-22
Also published as: CA3052345C; US20200009540A1; RU2019137486A3; CA3052345A1; RU2760904C2; RU2019137486A; AU2018264223B2; WO2018205787A1; ZA201905471B; AU2018264223A1; US11426712B2

Abstract

This disclosure relates to a kind of fischer-tropsch synthetic catalyst, its preparation method and its application in Fischer-Tropsch synthesis.Wherein, the catalyst is included：Active component, the active component is selected from least one of group viii b transition metal；Optional promoter metal；And the nitride carrier with high-specific surface area.The catalyst is characterised by that active metal is carried on the nitride carrier with high-ratio surface, and causes the active component high degree of dispersion in catalyst.The high-temperature stability that the catalyst has high hydrothermal stability, excellent resistance to mechanical wear resistance, high F- T synthesis are active and excellent.

Description

Fischer-tropsch synthetic catalyst comprising nitride carrier and its preparation method and application

Technical field

The invention belongs to heterogeneous catalysis, especially F- T synthesis catalytic field.Especially, the present invention relates to comprising new The fischer-tropsch synthetic catalyst of catalyst carrier, the preparation method of the catalyst and its application in Fischer-Tropsch synthesis.Specifically For, the present invention relates to will contain the group viii b gold being carried on the carrier obtained from nitride as catalyst carrier The new fischer-tropsch synthetic catalyst of category.

Background technology

Synthesis gas (contains CO and H₂, a small amount of CO₂, methane and N₂Gaseous mixture) in the presence of catalyst, can be converted into Hydrocarbon compound.This reaction is referred to as Fischer-Tropsch synthesis, and group viii b transition metal iron, cobalt, nickel, ruthenium are commonly used for this The active component of the catalyst of reaction.

Fischer-Tropsch synthesis is a kind of high temperature (150-350 DEG C), high pressure (10-50bar), strongly exothermic (165kJ/mol) Reaction.A kind of Main By product of the reaction is water.The reactor suitable for Fischer-Tropsch synthesis mainly has fixed bed, consolidated at present Determine fluid bed and gas-liquid-solid three phase slurry bed.Therefore, fischer-tropsch synthetic catalyst can undergo very harsh during the course of the reaction Mechanically and chemically stress, this requires catalyst to have very high wear resistance.

Some usual refractory oxides, as silica, aluminum oxide, titanium oxide and zirconium oxide etc., are used as F- T synthesis and urge The carrier of agent.But these carriers also bring some shortcomings being difficult to avoid that, such as lower thermal conductivity, hydrothermal stability to catalyst Difference, surface acidity are strong, mechanical strength is not high and antiwear property is poor etc..Because Fischer-Tropsch synthesis is strong exothermal reaction, catalysis The poor thermal conductivity of agent can cause a large amount of reaction heat in course of reaction to be stranded in inside catalyst granules, cause catalyst local reaction Overtemperature, target product selectivity are deteriorated, more serious meeting causes catalyst activity phase sintering to lose catalytic activity, therefore and time shift Except a large amount of reaction heat discharged inside catalyst granules become extremely important.In addition, the high moisture in Fischer-Tropsch synthesis Pressure is also very fatal for catalyst.Document (Journal of the Chemical Society-Chemical Communications, 1984,10, the 629-630 pages) report that water has very harmful shadow to the catalyst of alumina load Ring, depressed in low temperature, low moisture, carrying alumina, which is known from experience, is partially converted into plan water boehmite, and the latter can cause catalyst Efflorescence.To improve the mechanically and chemically stability of fischer-tropsch synthetic catalyst, numerous researchers, which attempt to find, has highly thermally conductive property, height The novel catalyst carrier of mass-transfer efficiency.

Hexagonal phase boron nitride is a kind of stratified material, has carried out Primary Study as the carrier of different catalysts at present. Such as, document (J.Catal., 2001,200, the 1-3 pages) reports a kind of Ba-Ru/BN catalyst and shown in ammonia synthesis reaction Unprecedented reactivity is shown, while without any inactivation behavior of generation in 3500h reaction time.Document (RSC Advances, 2016,6, the 38356-38364 pages) report a kind of hexagonal phase boron nitride load for Fischer-Tropsch synthesis Iron catalyst, although the catalyst shows preferable operation stability, but the phase of iron is with big crystal grain in the catalyst Based on the metallic iron of size, Fe active phase dispersion degree is relatively low, the active low, methane selectively of Fischer-Tropsch synthesis is higher, is unfavorable for Desired hydrocarbon compound (mainly C₅ ⁺Hydro carbons) large-scale production.Patent application CN 106179438A and document (ACS Catalysis, 2016,6, the 6814-6822 pages) report a kind of Ni@BN/SiO₂Core shell-type catalyst, the catalyst is in first Compared with common Ni/SiO in alkylation reaction₂Catalyst has the anti-caking power of higher high temperature active and Geng Gao, and presses down Make Carbon deposition and Ni is lost in, but SiO₂Carrier thermal conductivity itself is poor, therefore, and reaction heat retention can be made to a certain extent Inside catalyst granules adverse effect is brought for reaction system.Patent CN 104591106B and patent application CN 105293453A and CN 106179443A) disclose a variety of hexagonal phase boron nitride nanometer sheet preparation method and its as carry Body carried metal palladium catalyst, improves the dispersiveness and the catalytic activity in hydrogenation reaction of metal nanoparticle.

Silicon nitride (Si₃N₄) there is also tripartite's phase or hexagonal phase structure (tripartite's phase silicon nitride and hexagonal phase silicon nitride), it is former Sub- crystal.It is less as the research of catalyst carrier on silicon nitride.C.M é thivier et al. (Appl.Catal.A., 1999, 182, the 337-344 pages) silicon nitride is prepared for using CVD method, it is anti-for methane oxidation using it as carrier loaded palladium catalyst Should.Patent (WO 199920390) discloses one kind with specific surface area 8.8m²/ g silicon nitride is that carrier, palladium acetylacetonate are palladium Source, toluene are palladium catalyst prepared by solvent, for methane oxidation, and the catalyst is with being supported on α-Al₂O₃Palladium catalyst Compared to more preferable catalytic activity.Patent (CN 101767022B) discloses a kind of silicon nitride supported V III, IB races metal Catalyst, the catalyst be used for nitrous oxide.However, up to the present, silicon nitride is used as into fischer-tropsch synthetic catalyst The research of carrier have not been reported.

In addition, current commercialized BN or Si₃N₄Material has very low specific surface area, is not suitable as F- T synthesis The carrier of catalyst；Similarly, directly synthesized by chemical synthesis process Fe/BN (see in RSC Advances, 2016, 6, the 38356-38364 pages) or Ni/BN catalyst (see in ACS Catalysis, 2016,6, the 6814-6822 pages) exist Active mutually serious Sintering Problem, these critical defects limit the application of boron nitride or silicon nitride material in F- T synthesis.Cause This is, it is necessary to using different from disclosed BN or Si in the prior art₃N₄Material, to have given play to high thermal conductance, so that as taking During Tropsch synthesis catalyst carrier, it can effectively slow down the temperature fluctuation of beds, thus beneficial to fischer-tropsch synthetic catalyst The production capacity of catalyst is operated and is substantially improved under more harsh reaction condition.

The content of the invention

The purpose of the disclosure is that the drawbacks described above for overcoming existing fischer-tropsch synthetic catalyst to exist is used to synthesize there is provided one kind Gas prepares the fischer-tropsch synthetic catalyst of hydrocarbon compound, and the catalyst is greatly improved in terms of mass transfer and heat transfer, thus greatly The big efficiency for improving catalyst.The disclosure additionally provides preparation method and its answering in Fischer-Tropsch synthesis of the catalyst With.Specifically, the catalyst includes group viii b transition metal isoreactivity phase metal and boron nitride and/or nitridation silicon carrier.

Thus, present disclose provides a kind of fischer-tropsch synthetic catalyst, the catalyst can contain：Active phase metal is (for example, come From at least one of group viii b transition metal iron, cobalt, nickel, ruthenium), optional promoter metal, and by active phase metal and Optional promoter metal is carried on the boron nitride (preferably hexagonal phase boron nitride) selected from high-specific surface area, silicon nitride (preferred tripartite Phase silicon nitride, hexagonal phase silicon nitride) or the carrier of its mixture on.Wherein, the decentralization of active phase metal is very high, makes catalyst Show good catalyst activity.Moreover, the catalyst has excellent mass transfer and heat-transfer capability, it can greatly improve in row F- T synthesis performance in tubular fixed-bed reaction.

The disclosure is additionally provided with a kind of method for preparing above-mentioned catalyst, and methods described comprises the following steps：(1) prepare Specific surface area is not less than 80m²/ g nitride carrier；(2) using as the presoma of the active metal of active component and optionally The presoma of promoter metal be carried on the nitride carrier, form catalyst precursor；(3) by catalyst precursor into Type, the catalyst precursor after being molded；(4) catalyst precursor after shaping is dried and is calcined, obtain described Catalyst.

The carrier of the disclosure shows many beneficial characteristics in fischer-tropsch synthetic catalyst is prepared：High-termal conductivity, high ratio The high-specific surface area of surface area, resistance against physical chemical abrasion and high mechanical properties, the especially carrier can promote catalyst to live The high degree of dispersion of property phase and the activity for thus significantly improving catalyst.

The disclosure, which additionally provides above-mentioned fischer-tropsch synthetic catalyst, to be used to catalyze and synthesize gas in Fischer-Tropsch synthesis to make The purposes of standby hydrocarbon compound.Or, the disclosure additionally provides a kind of Fischer-Tropsch synthesis method, wherein, using above-mentioned Fischer-Tropsch Synthetic catalyst catalyzes and synthesizes gas to prepare hydrocarbon compound.Specifically, by synthesis gas be passed through in Fischer-Tropsch synthesis device with The catalyst is contacted, and is reacted to prepare hydrocarbon compound by the catalyst synthesis gas.

Test result indicates that, the cobalt that the boron nitride and/or silicon nitride of high-specific surface area are used as catalyst carrier and obtained The fischer-tropsch synthetic catalyst such as base or iron-based has obvious increased catalytic activity, long period stability and flexible operability, When the fischer-tropsch synthetic catalyst particularly being applied into high temperature fixed bed Fischer-Tropsch synthesis.The catalyst of the disclosure has excellent Heat, mass transfer ability, can prepare with high selectivity target hydrocarbon compound (particularly C₅ ⁺Hydro carbons, i.e. carbon number Hydrocarbon more than or equal to 5), and show good mechanically and chemically stability.Therefore, the catalyst is highly suitable for Fischer-Tropsch synthesis.The catalyst is particularly suitable for use in (having shell-heat exchange of heat pipe in conventional fixed bed reactors or shell-and-tube reactor Pattern) in and the Fischer-Tropsch synthesis that is carried out under the conditions of high-speed.

Brief description of the drawings

Fig. 1 is the XRD spectrum of hexagonal boron nitride carrier prepared by embodiment 1.

Fig. 2 is the XRD spectrum of boron nitride carrier prepared by embodiment 2.

Fig. 3 is the XRD spectrum of nitridation silicon carrier prepared by embodiment 3.

Fig. 4 is catalyst Exam-11a prepared by embodiment 11 XRD spectrum.

Fig. 5 is catalyst Exam-11b prepared by embodiment 11 XRD spectrum.

Fig. 6 is catalyst Exam-11c prepared by embodiment 11 XRD spectrum.

Embodiment

Herein, unless otherwise indicated, term " specific surface area " is represented by BET methods (Brunauer-Emmet- Teller) determine specific surface area, assay method referring to standard NFX 11-621 description.Herein, unless otherwise indicated, Term " catalyst activity phase ", " active component ", " active phase metal ", " active metal " and " metal active phase " is interchangeable makes With each meaning the metal ingredient of the active phase as fischer-tropsch synthetic catalyst.

The invention provides a kind of fischer-tropsch synthetic catalyst, wherein, the catalyst is included：Active component, the activearm It is divided into selected from least one of group viii b transition metal；Optional promoter metal；And nitride carrier, the carrier It is not less than 80m for specific surface area²/ g boron nitride, silicon nitride or its mixture；Wherein, the active component and optional auxiliary agent Metal Supported is on carrier.

It is preferred that, nitride carrier can be at nano-scale, and its shape can be nano particle, nanometer sheet, nanotube, nanometer Cage, nanofiber, nano wire etc..Additionally, it is preferred that the specific surface area of the nitride carrier is not less than 100m²/ g, preferably greater than 100m²/g.The decentralization of active component more preferably in the fischer-tropsch synthetic catalyst is 15%-75%, so that catalyst has There is more preferably catalytic activity.Boron nitride is preferably hexagonal phase boron nitride.Silicon nitride is preferably tripartite's phase silicon nitride and/or hexagonal phase Silicon nitride.

Active component (that is, active phase metal) is preferably selected from least one of iron, cobalt, nickel and ruthenium.Promoter metal is Selected from least one of manganese, chromium, zinc, molybdenum, copper, platinum, palladium, rhodium, iridium, gold, silver, magnesium, calcium, strontium, barium, sodium and potassium.

The mass ratio of active phase metal and carrier is (0.1~400):100.When active phase metal is selected from iron, cobalt and/or nickel When, the mass ratio of active phase metal and carrier is (1~400):100th, preferably (5~100):100th, more preferably (10~80): 100th, most preferably (20~50):100th, particularly preferably (30~40):100.When active phase metal be selected from ruthenium when, active phase metal with The mass ratio of carrier is (0.1~10):100th, preferably (0.5~8):100th, more preferably (1~6):100th, most preferably (3~5): 100。

The mass ratio of promoter metal and carrier is (2000ppm~60):100.Especially, when promoter metal be selected from manganese, chromium, When molybdenum and/or zinc, the mass ratio of promoter metal and carrier is (1~40):100th, preferably (5~30):100th, more preferably (10~ 20):100th, most preferably (15~20):100.When promoter metal is selected from copper, the mass ratio of promoter metal and carrier for (0.5~ 15):100th, preferably (1~10):100th, more preferably (2~6):100.When promoter metal is selected from platinum, palladium, rhodium, iridium, silver and/or gold When, the mass ratio of promoter metal and carrier is (0.002~1):100th, preferably (0.01~0.5):100th, more preferably (0.05~ 0.3):100th, it is most preferably (0.1~0.2):100.When promoter metal is selected from magnesium, calcium, strontium, barium, sodium and/or potassium, auxiliary agent gold The mass ratio of category and carrier is (0.5~15):100th, preferably (1~12):100th, more preferably (2~9):100.

Preferably, the active component in catalyst:Promoter metal:The mass ratio of carrier is (0.1~300):(0.002 ~30):100.

The disclosure additionally provides a kind of method for preparing above-mentioned catalyst, wherein, methods described comprises the following steps：(1) Prepare specific surface area and be not less than 80m²/ g nitride carrier；(2) using as the presoma of the active metal of active component and appoint The presoma of the promoter metal of choosing is carried on the nitride carrier, forms catalyst precursor；(3) by catalyst precursor Shaping, the catalyst precursor after being molded；(4) catalyst precursor after shaping is dried and is calcined, obtain institute State catalyst.

It is preferred that, in above-mentioned steps (1), the nitride carrier be boron nitride (preferably hexagonal phase boron nitride) carrier and/ Or silicon nitride (preferably tripartite's phase silicon nitride, hexagonal phase silicon nitride) carrier.It is preferred that, nitride carrier of the invention can pass through thermalization Learn synthetic method or be prepared by mechanical means.

Wherein, boron nitride carrier (including hexagonal phase boron nitride) can be prepared by following heat chemistry synthetic method, the party Method is related to the thermal chemical reaction of the mixture of the predecessor of boron, the predecessor of nitrogen and transistion metal compound in an inert atmosphere. More specifically, this method comprises the following steps：(a) boron is made in inert atmosphere in closing autoclave or pressurized reactor The mixture reaction of predecessor, the predecessor of nitrogen and transistion metal compound, synthesizes the crude product of nitrogen boron；(b) use respectively The crude product of mineral acid, the nitrogen boron of polar solvent leaching step (a) synthesis, obtains boron nitride powder；(c) dry, be calcined Boron nitride powder, obtains the boron nitride carrier.

Nitrogenizing silicon carrier can be prepared by following heat chemistry synthetic method, and this method is related to before the predecessor of silicon, nitrogen Drive the high-temperature liquid-phase reaction of the mixture of thing and solvent.More specifically, this method comprises the following steps：(a ') is in sealed high pressure React in the presence of organic solvent the mixture of the predecessor of silicon and the predecessor of nitrogen in kettle, synthesize the thick production of silicon nitride comprising Product；(b ') obtains the thick production of the silicon nitride comprising after pickling with the crude product of the silicon nitride comprising of mineral acid leaching step (a ') synthesis Product；(c ') washs, filtered the crude product of the silicon nitride comprising after the pickling with deionized water and solvent respectively, obtains silicon nitride powder Not；(d ') is dried, roasting alpha-silicon nitride powders, obtains the nitridation silicon carrier.

The predecessor of boron may be selected from boron oxide (B₂O₃), Boratex (Na₂B₄O₇), sodium borohydride (NaBH₄), boric acid (H₃BO₃), borine, borazine (H₆B₃N₃) or their any mixture, but it is not limited only to this.The predecessor of silicon may be selected from four Silicon chloride, tetraethyl orthosilicate, methyl silicate, silane, silane coupler, silicon imide or their any mixture, but not only It is limited to this.The predecessor of nitrogen may be selected from sodium azide, Sodamide, poly cyanamid, guanidine, urea, ammonia, borazine, ammonium chloride or it Any mixture, but be not limited only to this.Inert atmosphere can for nitrogen atmosphere, argon gas atmosphere, helium atmosphere or they Any mixed atmosphere, but it is not limited only to this.Transistion metal compound may be selected from Fe₂O₃、Fe₃O₄, anhydrous FeCl₃、Co₂O₃、Co₃O₄、 CoO, anhydrous CoCl₂, NiO or their any mixture, but be not limited only to this.Polar solvent in step (b) may be selected from water, Methanol, ethanol, propyl alcohol, tetrahydrofuran, dimethylformamide or their any mixture, but it is not limited only to this.

The predecessor of boron, the predecessor of nitrogen and transistion metal compound can be mixed using mechanical mixture mode and be formed mixing Thing, in the mixture, the atomic ratio of nitrogen and boron is 2:1 to 6:1st, preferably 3:1 to 5:1st, most preferably 3.5:1 to 4.5:1.Transition The atomic ratio of metal and boron may be, for example, 0.02:1 to 0.5:1.

In step (a), the mixture of the predecessor of boron, the predecessor of nitrogen and transistion metal compound can be made in following bar Reacted under part：Temperature is 400~1100 DEG C, preferably 600~1000 DEG C, most preferably 800~900 DEG C；It is preferred that pressure is 0.2 ~10MPa, preferably 0.5~5MPa.The further preferred reaction time is 1~20h, preferably 10~12h.

Mineral acid can be selected from hydrochloric acid, sulfuric acid, nitric acid, but be not limited only to this.The concentration of mineral acid be 0.1~5mol/L, It is preferred that 0.5~2.5mol/L, most preferably 1.0~1.5mol/L.

Organic solvent in step (a ') may be selected from benzene,toluene,xylene, ethylbenzene, hexane, heptane, octane, nonane, liquid Body paraffin, trioctylamine or their any mixture, but it is not limited only to this.Predecessor and the forerunner of nitrogen in the silicon of step (a ') In the mixture of thing, the atomic ratio of nitrogen and silicon is (0.01~10):1st, it is preferably (0.1~5):1st, optimal is (0.2~1):1. The volume ratio of the predecessor of organic solvent and silicon in step (a ') is (0.1-10):1st, preferably (0.5~5):1st, most preferably (1 ~2):1.In step (a '), the predecessor of silicon and the mixture of the predecessor of nitrogen can be made to be reacted under the following conditions：Temperature Spend for 300~600 DEG C, preferably 400~500 DEG C；It is preferred that pressure is 0.2~10MPa, preferably 0.5~5MPa.And then preferably react Time is 1~20h, preferably 5~10h.In step (c '), solvent may be selected from but be not limited to methanol, ethanol, propyl alcohol, tetrahydrochysene furan Mutter, dimethylformamide or their any mixture.

Boron nitride powder or alpha-silicon nitride powders can be dried and be calcined in air, inert atmosphere or vacuum.Dry Temperature can be 20~150 DEG C, preferably 80-150 DEG C；It is preferred that the dry time can be 1~24h, preferably 8~12h.The temperature of roasting Degree can be 250~650 DEG C, preferably 350~600 DEG C, most preferably 450~550 DEG C；It is preferred that the time being calcined may be, for example, 1~6h.

As a kind of exemplary embodiment, the boron nitride and nitridation silicon carrier of the disclosure can also pass through mechanical means Prepare, this method, which is related to, obtains the boron nitride and silicon nitride of common low specific surface area using the modes such as ball milling, ultrasound are broken Specific surface area is more than or equal to 80m²/ g boron nitride or nitridation silicon carrier.For example, the hexagonal phase boron nitride of the disclosure or tripartite Mutually or hexagonal phase nitridation silicon carrier can be using mechanical means (such as ball milling) by by commercialized hexagonal phase boron nitride, San Fangxiang Silicon nitride or hexagonal phase silicon nitride are ground to specific surface area more than or equal to 80m²It is prepared by/g.

As preferred example, in above-mentioned steps (2), the presoma of active metal and the presoma of promoter metal can lead to Cross the methods such as dipping, co-precipitation, water/solvent-thermal process, chemical vapor deposition and/or ald and be carried on nitride carrier On.

As the example of dipping method, the presoma of active metal and the presoma of promoter metal can by co-impregnation or point The method of step dipping is carried on nitride carrier under arbitrary temp, such as room temperature (such as 15 DEG C -40 DEG C).Wherein, it is exemplary Co-impregnation method include the presoma of active metal and the presoma of promoter metal by their ratio of components in the catalyst Example, which is mixed and is dissolved in solvent, forms dipping solution, and then dipping solution is impregnated on nitride carrier.Exemplary point Step dipping method is that the presoma of the presoma of active metal and promoter metal is dissolved separately in solvent to form individually leaching Stain solution, then step impregnation is on nitride carrier.Wherein, dipping can be incipient impregnation or excessive dipping. Incipient impregnation refers to that the volume of dipping solution is equal with pore volume；Excessive dipping refers to that the volume of dipping solution is more than and carried Pore volume.For example, can by by hexagonal phase boron nitride, tripartite's phase silicon nitride, hexagonal phase silicon nitride or their mixture with The dipping solution co-impregnation or step impregnation formed by the presoma of active metal and the presoma of promoter metal, and make active gold Category and promoter metal are carried on nitride carrier.

The solvent for forming dipping solution can be water, methanol, methylamine, dimethylamine, N,N-dimethylformamide, N- methyl formyls Amine, formamide, ethanol, ethylene glycol, ether, ethamine, acetonitrile, acetamide, propyl alcohol, acetone, propionitrile, tetrahydrofuran, dioxane, Butanol, pyridine, morpholine, quinoline, toluene, dimethylbenzene, heptane or their any mixture, but it is not limited only to this.

Or, the presoma of the presoma of active metal and promoter metal can be converted into by hydronium(ion) by coprecipitation method Oxide and oxide form and be deposited on nitride carrier.Wherein, exemplary coprecipitation method is included active metal Presoma and the presoma of promoter metal mix and be dissolved in solvent by their proportion of composing in the catalyst and form mixed Close salting liquid；The mixing salt solution is mixed and stirred for by catalyst proportion of composing with nitride support powder, uniform point is formed Scattered suspension；Suspension is mixed with alkaline sedimentation agent solution, precipitated, is stood, is filtered, washs and obtains catalyst precursor. For example, can be by by mixing salt solution and hexagonal phase boron nitride, tripartite's phase silicon nitride, hexagonal phase silicon nitride or their mixture Suspension is formed, is then co-precipitated with alkaline sedimentation agent solution, and active metal and promoter metal is carried on nitride carrier On.

Alkaline sedimentation agent solution can be alkali hydroxide soln, the water of such as sodium hydroxide and/or potassium hydroxide Solution；Can also be alkali carbonate or bicarbonate solution, such as sodium carbonate, sodium acid carbonate, potassium carbonate and/or saleratus The aqueous solution；It can also be ammonia spirit, ammonium carbonate solution, ammonium bicarbonate aqueous solution, preferably ammonia spirit.

Or, the presoma of active metal and the presoma of promoter metal can be converted by water/solvent process for thermosynthesizing It is deposited on for metal, hydration metal hydroxides, hydrated metal oxide etc. on nitride carrier.For example, can be by that will live Property metal presoma and presoma and the hexagonal phase boron nitride of promoter metal, tripartite's phase silicon nitride, hexagonal phase silicon nitride or it Mixture form mixed liquor in a solvent and enter water-filling/solvent-thermal process, active metal and promoter metal is carried on nitridation On thing carrier.

Form mixing salt solution or alkali hydroxide soln or alkali metal carbonate solution or alkali metal carbon above Sour hydrogen salt solution and the solvent that is used in water/solvent process for thermosynthesizing can be water, methanol, methylamine, dimethylamine, N, N- dimethyl Formamide, N-METHYLFORMAMIDE, formamide, ethanol, ethylene glycol, ethamine, acetonitrile, acetamide, propyl alcohol, propionitrile, tetrahydrofuran, two The ring of oxygen six, butanol, pyridine, morpholine, quinoline or their any mixture, but it is not limited only to this.

Or, the presoma of the presoma of active metal and promoter metal can be converted into by chemical gaseous phase depositing process Metal, metal carbides, metal nitride, metal oxide etc. and be deposited on nitride carrier.For example, can be by the way that work will be contained Property metal and the organo-metallic compound of promoter metal are in high vacuum (10^-1Pa-10^-6) or normal pressure (that is, one atmospheric pressure) bar Pa Heated under part, and make through chemical vapor deposition active metal and promoter metal be deposited on hexagonal phase boron nitride as carrier, On tripartite's phase silicon nitride, hexagonal phase silicon nitride or their mixture.

Or, the presoma of active metal and promoter metal can be converted into by metal, metal by Atomic layer deposition method Carbide, metal nitride, metal oxide etc. and be deposited on nitride carrier.For example, can be by high vacuum (10^-1Pa- 10^-6Pa) gaseous compound and oxidant of the alternating sorbent containing active metal and promoter metal in cabin, with Atomic layer deposition method Active metal and promoter metal are deposited on the hexagonal phase boron nitride as carrier, tripartite's phase silicon nitride, hexagonal phase silicon nitride or On their mixture.

The presoma of active metal is selected from following one or more：Ferric nitrate (preferably Fe(NO3)39H2O), chlorination Iron (preferably ferric chloride hexahydrate), frerrous chloride, ferrous sulfate, ferrous acetate, ferric acetyl acetonade (III), carbonyl iron, two cyclopentadienyls Iron, cobalt nitrate (preferably cabaltous nitrate hexahydrate), cobalt chloride (preferably cobalt chloride hexahydrate), cobaltous formate, cobalt acetate, acetylacetone,2,4-pentanedione Cobalt, carbonyl cobalt, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate, carbonyl nickel, ruthenic chloride, nitric acid ruthenium, triphenyl Phosphine chlorination ruthenium, carbonyl ruthenic chloride, chlorination ruthenic acid ammonium, nitrosyl nitric acid ruthenium, but it is not limited only to this.

The presoma of promoter metal is selected from following one or more：Manganese nitrate, manganese chloride, manganese acetate, acetylacetone,2,4-pentanedione Manganese, manganese carbonyl, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zinc acetylacetonate, chromic nitrate, chromium chloride, chromium sulfate, ammonium molybdate (preferably ammonium heptamolybdate), platinum chloride, platinum nitrate, chloroplatinic acid, ammonium chloroplatinate, the ammonium of nitroso two close platinum, rhodium nitrate, radium chloride, sulphur Sour rhodium, rhodium acetate, triphenylphosphine radium chloride, acetylacetonatodicarrhodium rhodium, palladium nitrate, palladium bichloride, palladium sulfate, acetic acid Palladium, tetrachloro-palladium acid ammonium, six ammonium chloropalladates, triphenylphosphine palladium, chloro-iridic acid, iridium chloride, acetic acid iridium, ammonium chloroiridate, chlorauride, chlorine gold Acid, ammonium chloraurate, silver nitrate, silver acetate, silver carbonate, magnesium nitrate, magnesium chloride, magnesium acetate, calcium nitrate, calcium chloride, calcium acetate, nitre Sour strontium, strontium chloride, strontium acetate, sodium nitrate, sodium chloride, sodium acetate, sodium hydroxide, sodium carbonate, sodium acid carbonate, potassium nitrate, chlorination Potassium, potassium hydroxide, potassium carbonate, saleratus, potassium acetate, but it is not limited only to this.

Before step (3), the catalyst precursor in step (2) can be dried and is calcined.

As preferred example, in above-mentioned steps (3), catalyst precursor can be by selected from being spray-dried, be compressed into In type, rotational forming, extruded moulding or oil shaping etc. forming method and be molded.It is preferred that the catalyst precursor after shaping can be located In graininess, microspheroidal, sheet, strip, column, ring-type, porous flake, trilobes.

As preferred example, in above-mentioned steps (4), the drying of the catalyst precursor after shaping can be in air, non- Carried out in reactive atmosphere or vacuum.It is preferred that dry temperature is 20~150 DEG C, preferably 80-150 DEG C.It is preferred that the dry time is 1 ~24h, preferably 8~12h.In certain embodiments, the catalyst precursor after shaping can carry out the drying of more than 2 times.Enter one Step is preferred, and the catalyst precursor after shaping can be calcined under inert atmosphere or oxidizing atmosphere.It is preferred that the temperature being calcined For 250~650 DEG C, preferably 350~600 DEG C, most preferably 450~550 DEG C.It is preferred that the time being calcined can be 1~6h.For example, into Catalyst precursor after type can carry out the roasting of more than 2 times.

The disclosure, which further relates to above-mentioned catalyst, to be used to catalyze and synthesize gas in Fischer-Tropsch synthesis to prepare hydrocarbon compound Purposes.Or, the disclosure further relates to a kind of Fischer-Tropsch synthesis method, wherein, it is catalyzed using above-mentioned fischer-tropsch synthetic catalyst Synthesis gas carries out Fischer-Tropsch synthesis to prepare hydrocarbon compound.

As preferred example, before the catalyst of the present invention is applied to Fischer-Tropsch synthesis, the catalysis is made in advance Agent is reduced in reducing atmosphere.Reducing atmosphere can be pure hydrogen atmosphere, CO atmosphere, synthesis gas atmosphere, ammonia atmosphere, dilution Hydrogen atmosphere, dilution CO atmosphere, dilution synthesis gas atmosphere, dilution ammonia atmosphere.H in synthesis gas₂With CO body Product is than being 0.01:1 to 1000:1.It can also further contain nitrogen in addition to corresponding each reducing atmosphere in each reducing atmosphere of dilution Gas, argon gas, helium, CO₂And CH₄, the volumetric concentration of the reducibility gas in each atmosphere preferably diluted is more than 10%, preferably big In 25%, more preferably 50%, be most preferably 75%, be most preferably more than 90%.Fischer-tropsch synthetic catalyst is by further reduction With certain reduction degree, (that is, metal phase, metal carbides, metal nitride account for the percentage of all active phase metals for processing generation Number) reduction-state fischer-tropsch synthetic catalyst.It is preferred that the reduction degree of obtained reduction-state fischer-tropsch synthetic catalyst at least above 60%, Preferably greater than 75%, most preferably it is more than 85%.In addition, the tenor in catalyst precursor or catalyst can be using known normal Rule elemental analysis method is measured, such as ICP-AES, X-ray fluorescence spectra etc..The reduction degree of catalyst can be using known Temperature programming method is determined, so that the reduction degree of cobalt-base catalyst is determined as an example：(1) in 10%H₂In it is steady with 10 DEG C/min speed Surely the temperature of catalyst sample is raised to reduction temperature (400 DEG C), and keeps 6h, and H is determined with TCD or MS detectors₂Consumption Curve, labeled as TPR1；(2) after reduction process terminates, without cooling, with 10 DEG C/min speed in identical reducing atmosphere 1000 DEG C are stably heated the sample to, and keeps 10min, H is obtained₂Consumption curve TPR2；(3) TPR1 and TPR2 is accumulated respectively Point, obtain the H of two curves₂Consumption, TPR1/ (TPR1+TPR2) is the reduction degree (as a percentage) of catalyst.Reduction After end, because the active metal in catalyst is active to the oxygen in air, catalyst seal can be stored in wax-like heavy Matter hydrocarbon (that is, carbon number be more than 18 saturated straight chain alkane and its mixture) in or be transferred in Fischer-Tropsch synthesis device.

H in the synthesis gas of Fischer-Tropsch synthesis₂Volume ratio with CO is 0.5:1 to 3.0:1st, preferably 1.0:1 to 2.5: 1st, more preferably 1.2:1 to 2.2:1st, most preferably 1.5:1 to 2.0:1.Fischer-Tropsch synthesis can be with continous way or intermittent reaction Process is carried out.Fischer-Tropsch synthesis can use one or more fixed bed reactors, micro passage reaction, continuously stir slurry bed system Tank reactor, jet-loop formula reactor, gas holdup reactor or fluidized-bed reactor are carried out.Fischer-Tropsch synthesis Pressure is 1.0~6.0MPa, and temperature is 120~350 DEG C.When Fischer-Tropsch synthesis is carried out with continuous reaction process, reaction Air speed is 100~60000NL/Kg/h.

For example, when fischer-tropsch synthetic catalyst is Co catalysts, the H in synthesis gas₂Volume ratio with CO is 1.0:1 to 3.0:1st, it is preferably 1.5:1 to 2.5:1st, most preferably 1.8:1 to 2.2:1.It is preferred that the pressure of Fischer-Tropsch synthesis be 1.0~ 6.0MPa, preferably 1.5~4.5MPa, optimal 2.0~3.0MPa.It is preferred that the temperature of Fischer-Tropsch synthesis be 150~280 DEG C, it is excellent Select 180~260 DEG C, optimal 200~240 DEG C.When Fischer-Tropsch synthesis is carried out with continuous reaction process, reaction velocity is 100~25000NL/Kg/h, preferably 1000~20000NL/Kg/h, optimal 5000~10000NL/Kg/h.Or, for example, working as When fischer-tropsch synthetic catalyst is iron catalyst, the H in synthesis gas₂Volume ratio with CO is 0.5:1 to 3.0:1st, preferably 1.0:1 to 2.5:1st, more preferably 1.2:1 to 2.2:1st, most preferably 1.5:1 to 2.0:1.It is preferred that the pressure of Fischer-Tropsch synthesis be 1.0~ 6.0MPa, preferably 1.5~5.5MPa, more preferably 2.0~5.0MPa, most preferably 2.5~4.0MPa.It is preferred that Fischer-Tropsch synthesis Temperature is 220~350 DEG C, preferably 240~330 DEG C, optimal 260~300 DEG C.When Fischer-Tropsch synthesis is with continuous reaction process During progress, reaction velocity is 100~60000NL/Kg/h, preferably 1000~40000NL/Kg/h, optimal 10000~20000NL/ Kg/h。

Exemplary arrangement described in the disclosure has following features：Method for preparing catalyst is simple, raw material is cheap, be produced into This is low, reproducible；There is the catalyst of the disclosure larger specific surface area (to be not less than 80m²/ g), the active metal of superelevation point (abrasion index is 1~2.0%h for divergence (15%-75%), higher mechanical strength^-1), higher heat endurance and good The mutually anti-caking power of metal active；The catalyst of the disclosure is when applied to Fischer-Tropsch synthesis, compared with direct chemical synthesis system Standby catalyst includes conventional carrier (SiO₂Or Al₂O₃) catalyst, with more preferable synthesis gas activity of conversion, hydro carbons Compound selectivity and high-temperature stability.

For example, the cobalt-base catalyst comprising boron nitride or nitridation silicon carrier of the disclosure is 230~250 DEG C in reaction temperature And when reaction velocity is 10000NL/Kg/h, CO conversion ratio can maintain more than 10%, C₅ ⁺The selectivity of hydrocarbon is more than 85%, Methane selectively is less than 8%.CO is converted to be tested after more than 100h stable operation：Initial reaction temperature is 220 DEG C, and reinforcing is surveyed It is 250 DEG C to try temperature.The conversion stability maintenance of the catalyst more than 0.8, even greater than 0.9.For another example the bag of the disclosure The ferrum-based catalyst of nitrogen boron or nitridation silicon carrier is in reaction temperature for 280~320 DEG C and in reaction velocity in 15000NL/ During more than Kg/h, CO conversion ratio is able to maintain that more than 10%, CO₂Selectivity is less than 10% (being even less than 5%), C₅ ⁺Hydrocarbon Selectivity is more than 90%, and methane selectively is less than 5%.CO is converted to be tested after more than 100h stable operation：Initial reaction temperature Spend for 280 DEG C, reinforcing reaction temperature is 300 DEG C.The conversion stability maintenance of the catalyst more than 0.8, even greater than 0.9.

Herein, unless otherwise indicated, term " conversion stability " is defined as CO initially compared with low temperature (initial reaction temperature Degree) under first conversion ratio returned to by catalyst after the higher reaction temperatures (accelerated test temperature) of experience a period of time it is initial The whole conversion ratio obtained during reaction temperature be divided by gained business (that is, final state activity divided by initial activity obtained by business or percentage Number).

Present disclosure can exemplarily be illustrated by the record in numbering paragraph as follows：

1. a kind of fischer-tropsch synthetic catalyst, wherein, the catalyst is included：Active component, the active component be selected from At least one of group viii b transition metal；Optional promoter metal；And nitride carrier, the carrier is than surface Product is not less than 80m²/ g boron nitride, silicon nitride or its mixture；

Wherein, the active component and optional promoter metal are carried on the carrier.

2. the catalyst according to paragraph 1, wherein, the decentralization of the active component is 15%-75%.

3. the catalyst according to paragraph 1 or 2, wherein, the active component be in iron, cobalt, nickel and ruthenium extremely Few one kind.

4. the catalyst according to any one of paragraph 1-3, wherein, the promoter metal is selected from including following group At least one of：Manganese, chromium, zinc, molybdenum, copper, platinum, palladium, rhodium, iridium, gold, silver, magnesium, calcium, strontium, barium, sodium and potassium.

5. the catalyst according to any one of paragraph 1-4, wherein, the specific surface area of the carrier is not less than 100m²/ G, preferably greater than 100m²/g。

6. the catalyst according to any one of paragraph 1-5, wherein, the boron nitride is hexagonal phase boron nitride.

7. the catalyst according to any one of paragraph 1-6, wherein, the silicon nitride be tripartite's phase silicon nitride and/or Hexagonal phase silicon nitride.

8. the catalyst according to any one of paragraph 1-7, wherein, the carrier is shaped as nano particle, nanometer Piece, nanotube, nanocages, nanofiber and/or nano wire.

9. the catalyst according to any one of paragraph 1-8, wherein, the active component and the mass ratio of the carrier For (0.1~400):100.

10. the catalyst according to any one of paragraph 1-9, wherein, the active component is in iron, cobalt and nickel At least one, the mass ratio of the active component and the carrier is (1~400):100th, preferably (5~100):100th, it is more excellent Select (10~80):100th, most preferably (20~50):100th, particularly preferably (30~40):100.

11. the catalyst according to any one of paragraph 1-9, wherein, the active component is ruthenium, the active component Mass ratio with the carrier is (0.1~10):100th, preferably (0.5~8):100th, more preferably (1~6):100th, most preferably (3 ~5):100.

12. the catalyst according to any one of paragraph 1-11, wherein, the promoter metal and the quality of the carrier Than for (2000ppm~60):100.

13. the catalyst according to any one of paragraph 1-12, wherein, the promoter metal be selected from manganese, chromium, molybdenum and The mass ratio of at least one of zinc, the promoter metal and the carrier is (1~40):100th, preferably (5~30):100th, more It is preferred that (10~20):100th, most preferably (15~20):100.

14. the catalyst according to any one of paragraph 1-12, wherein, the promoter metal is copper, the auxiliary agent gold The mass ratio of category and the carrier is (0.5~15):100th, preferably (1~10):100th, more preferably (2~6):100.

15. the catalyst according to any one of paragraph 1-12, wherein, the promoter metal be selected from platinum, palladium, rhodium, The mass ratio of at least one of iridium, silver and gold, the promoter metal and the carrier is (0.002~1):100th, preferably (0.01~0.5):100th, more preferably (0.05~0.3):100th, it is most preferably (0.1~0.2):100.

16. the catalyst according to any one of paragraph 1-12, wherein, the promoter metal be selected from magnesium, calcium, strontium, The mass ratio of at least one of barium, sodium and potassium, the promoter metal and the carrier is (0.5~15):100th, preferably (1~ 12):100th, more preferably (2~9):100.

17. the catalyst according to any one of paragraph 1-9 and 12, wherein, the active metal:Auxiliary agent:Carrier Mass ratio is (0.1~300):(0.002~30):100.

18. the method for the fischer-tropsch synthetic catalyst any one of paragraph 1-17 is prepared, wherein, methods described is included such as Lower step：(1) prepare specific surface area and be not less than 80m²/ g nitride carrier；(2) active metal of active component will be used as Presoma and the presoma of optional promoter metal are carried on the nitride carrier, form catalyst precursor；(3) by institute State that complex catalyst precursor is body formed, the catalyst precursor after being molded；(4) catalyst precursor after the shaping is carried out Dry and be calcined, obtain the catalyst.

19. the method according to paragraph 18, wherein, the nitride carrier is that boron nitride carrier and/or silicon nitride are carried Body.

20. the method according to paragraph 18 or 19, wherein, the nitride carrier be hexagonal phase boron nitride carrier and/ Or tripartite's phase silicon nitride or hexagonal phase nitridation silicon carrier.

21. the method according to any one of paragraph 18-20, in step (1), is closed by mechanical means or heat chemistry The nitride carrier is prepared into method.

22. the method according to paragraph 21, wherein, the nitride carrier is boron nitride carrier, and the boron nitride is carried Body is prepared by the heat chemistry synthetic method comprised the following steps：(a) in nonactive in closing autoclave or pressurized reactor React the mixture of the predecessor of boron, the predecessor of nitrogen and transistion metal compound in atmosphere, synthesize the thick production of nitrogen boron Product；(b) crude product of the nitrogen boron synthesized respectively with mineral acid, polar solvent leaching step (a), obtains boron nitride powder Not；(c) dry, be calcined the boron nitride powder, obtain the boron nitride carrier.

23. the method according to paragraph 22, wherein, the predecessor of the boron is selected from boron oxide, Boratex, hydroboration Sodium, boric acid, borine, borazine or their any mixture.

24. the method according to paragraph 22 or 23, wherein, the transistion metal compound is selected from Fe₂O₃、Fe₃O₄, nothing Water FeCl₃、Co₂O₃、Co₃O₄, CoO, anhydrous CoCl₂, NiO or their any mixture.

25. the method according to any one of paragraph 22-24, wherein, the inert atmosphere can be nitrogen atmosphere, argon Gas atmosphere, helium atmosphere or their any mixed atmosphere.

26. the method according to any one of paragraph 22-25, wherein, the predecessor of the boron, the predecessor of nitrogen and mistake Metallic compound is crossed to mix using mechanical mixture mode and form mixture.

27. the method according to any one of paragraph 22-26, in step (a), in the mixture, the nitrogen Atomic ratio with boron is 2:1 to 6:1st, preferably 3:1 to 5:1st, most preferably 3.5:1 to 4.5:1.

28. the method according to any one of paragraph 22-27, in step (a), in the mixture, the mistake The atomic ratio for crossing metal and boron is 0.02:1 to 0.5:1.

29. the method according to any one of paragraph 22-28, in step (a), the reaction temperature of the mixture is 400~1100 DEG C, preferably 600~1000 DEG C, most preferably 800~900 DEG C；It is preferred that reaction pressure is 0.2~10MPa, preferably 0.5 ~5MPa.

30. the method according to any one of paragraph 22-29, in step (a), the reaction time of the mixture is 1~20h, preferably 10~12h.

31. the method according to any one of paragraph 22-30, in step (b), the polar solvent is selected from water, first Alcohol, ethanol, propyl alcohol, tetrahydrofuran, dimethylformamide or their any mixture.

32. the method according to paragraph 21, wherein, the nitride carrier is nitridation silicon carrier, and the silicon nitride is carried Body is prepared by the heat chemistry synthetic method comprised the following steps：(a ') is in sealed autoclave in the presence of organic solvent The mixture of the predecessor of silicon and the predecessor of nitrogen is reacted, the crude product of silicon nitride comprising is synthesized；(b ') is walked with mineral acid leach Suddenly the crude product of the silicon nitride comprising of (a ') synthesis, obtains the crude product of the silicon nitride comprising after pickling；(c ') spend respectively from Sub- water and solvent washing, the crude product for filtering the silicon nitride comprising after the pickling, obtain silicon nitride powder；(d ') is dried, roasting The alpha-silicon nitride powders, obtain the nitridation silicon carrier.

33. the method according to paragraph 32, wherein, the predecessor of the silicon is selected from silicon tetrachloride, tetraethyl orthosilicate, just Methyl silicate, silane, silane coupler, silicon imide or their any mixture.

34. the method according to paragraph 32 or 33, wherein, in step (a '), the organic solvent is selected from benzene, first Benzene, dimethylbenzene, ethylbenzene, hexane, heptane, octane, nonane, atoleine, trioctylamine or their any mixture.

35. the method according to any one of paragraph 32-34, wherein, in step (a '), in the mixture, The atomic ratio of the nitrogen and silicon is (0.01~10):1st, it is preferably (0.1~5):1st, optimal is (0.2~1):1.

36. the method according to any one of paragraph 32-35, wherein, in step (a '), the organic solvent and institute The volume ratio for stating the predecessor of silicon is (0.1-10):1st, preferably (0.5~5):1st, most preferably (1~2):1.

37. the method according to any one of paragraph 32-36, wherein, in step (a '), the reaction of the mixture Temperature is 300~600 DEG C, preferably 400~500 DEG C；It is preferred that reaction pressure is 0.2~10MPa, preferably 0.5~5MPa.

38. the method according to any one of paragraph 32-37, wherein, in step (a '), the reaction of the mixture Time is 1~20h, preferably 5~10h.

39. the method according to any one of paragraph 32-38, wherein, in step (c '), the solvent is selected from first Alcohol, ethanol, propyl alcohol, tetrahydrofuran, dimethylformamide or their any mixture.

40. the method according to any one of paragraph 22-39, wherein, the predecessor of the nitrogen may be selected from sodium azide, Sodamide, poly cyanamid, guanidine, urea, ammonia, borazine, ammonium chloride or their any mixture.

41. the method according to any one of paragraph 22-40, wherein, the mineral acid is selected from hydrochloric acid, sulfuric acid, nitric acid.

42. the method according to paragraph 41, wherein, the concentration of the mineral acid is 0.1~5mol/L, preferably 0.5~ 2.5mol/L, most preferably 1.0~1.5mol/L.

43. the method according to any one of paragraph 22-42, wherein, the boron nitride powder or the silicon nitride powder End is dried and is calcined in air, inert atmosphere or vacuum.

44. the method according to any one of paragraph 22-43, described in the step (c) and the step (d ') Dry temperature is 20~150 DEG C, preferably 80-150 DEG C；It is preferred that the time of the drying can be 1~24h, preferably 8~12h.

45. the method according to any one of paragraph 22-44, described in the step (c) and the step (d ') The temperature of roasting is 250~650 DEG C, preferably 350~600 DEG C, most preferably 450~550 DEG C；It is preferred that the time of the roasting is 1~6h.

46. the method according to paragraph 21, wherein, obtain the nitride carrier by using ball milling or ultrasonication.

47. the method according to any one of paragraph 18-46, wherein, presoma and the auxiliary agent gold of the active metal The presoma of category is loaded by the method for dipping, co-precipitation, water/solvent-thermal process, chemical vapor deposition and/or ald In on the nitride carrier.

48. the method according to any one of paragraph 18-47, wherein, the presoma of the active metal is selected from such as Under one or more：Ferric nitrate (preferably Fe(NO3)39H2O), iron chloride (preferably ferric chloride hexahydrate), frerrous chloride, sulphur Sour ferrous iron, ferrous acetate, ferric acetyl acetonade (III), carbonyl iron, ferrocene, cobalt nitrate (preferably cabaltous nitrate hexahydrate), cobalt chloride (preferably cobalt chloride hexahydrate), cobaltous formate, cobalt acetate, acetylacetone cobalt, carbonyl cobalt, nickel nitrate, nickel chloride, nickel sulfate, acetic acid Nickel, nickel acetylacetonate, carbonyl nickel, ruthenic chloride, nitric acid ruthenium, triphenylphosphine chlorination ruthenium, carbonyl ruthenic chloride, chlorination ruthenic acid ammonium, Nitrosyl nitric acid ruthenium.

49. the method according to any one of paragraph 18-48, wherein, the presoma of the promoter metal is selected from such as Under one or more：Manganese nitrate, manganese chloride, manganese acetate, manganese acetylacetonate, manganese carbonyl, zinc nitrate, zinc chloride, zinc sulfate, vinegar Sour zinc, zinc acetylacetonate, chromic nitrate, chromium chloride, chromium sulfate, ammonium molybdate (preferably ammonium heptamolybdate), platinum chloride, platinum nitrate, chlorine platinum Acid, ammonium chloroplatinate, the ammonium of nitroso two close platinum, rhodium nitrate, radium chloride, rhodium sulfate, rhodium acetate, triphenylphosphine radium chloride, levulinic Ketone triphenylphosphine rhodium carbonyl, palladium nitrate, palladium bichloride, palladium sulfate, palladium, tetrachloro-palladium acid ammonium, six ammonium chloropalladates, triphenylphosphine Palladium, chloro-iridic acid, iridium chloride, acetic acid iridium, ammonium chloroiridate, chlorauride, gold chloride, ammonium chloraurate, silver nitrate, silver acetate, silver carbonate, Magnesium nitrate, magnesium chloride, magnesium acetate, calcium nitrate, calcium chloride, calcium acetate, strontium nitrate, strontium chloride, strontium acetate, sodium nitrate, sodium chloride, Sodium acetate, sodium hydroxide, sodium carbonate, sodium acid carbonate, potassium nitrate, potassium chloride, potassium hydroxide, potassium carbonate, saleratus, acetic acid Potassium.

50. the method according to any one of paragraph 18-49, wherein, will be in step (2) before the step (3) The catalyst precursor of middle formation is dried and is calcined.

51. the method according to any one of paragraph 18-50, wherein, in the step (3), before the catalyst Body is driven by being molded selected from following forming method：In spray drying, compression forming, rotational forming, extruded moulding or oil into Type.

52. the method according to any one of paragraph 18-51, wherein, the catalyst precursor after the shaping is in Graininess, microspheroidal, sheet, strip, column, ring-type, porous flake, trilobes.

53. the method according to any one of paragraph 18-52, wherein, the catalyst precursor after the shaping is existed It is dried in air, inert atmosphere or vacuum.

54. the method according to any one of paragraph 18-53, in the step (4), the temperature of the drying is 20 ~150 DEG C, preferably 80-150 DEG C；It is preferred that the time of the drying is 1~24h, preferably 8~12h.

55. the method according to any one of paragraph 18-54, in the step (4), by the catalysis after the shaping Agent presoma carries out the drying of more than 2 times.

56. the method according to any one of paragraph 18-55, wherein, the catalyst precursor after the shaping is existed It is calcined under inert atmosphere or oxidizing atmosphere.

57. the method according to any one of paragraph 18-56, in the step (4), the temperature of the roasting is 250~650 DEG C, preferably 350~600 DEG C, most preferably 450~550 DEG C；It is preferred that the time of the roasting is 1~6h.

58. the method according to any one of paragraph 18-57, wherein, the catalyst precursor after the shaping is entered The roasting that row is more than 2 times.

59. the fischer-tropsch synthetic catalyst any one of paragraph 1-17 is used to catalyze and synthesize gas in Fischer-Tropsch synthesis To prepare the purposes of hydrocarbon compound.

60. the purposes according to paragraph 59, wherein, before the catalyst is applied to Fischer-Tropsch synthesis, in advance The catalyst is first set to be reduced in reducing atmosphere.

61. the purposes according to paragraph 60, wherein, the reducing atmosphere is selected from pure hydrogen atmosphere, CO atmosphere, synthesis gas Atmosphere, ammonia atmosphere, the hydrogen atmosphere of dilution, the CO atmosphere of dilution, the synthesis gas atmosphere of dilution, the ammonia atmosphere of dilution.

62. the purposes according to paragraph 61, wherein, the H in the synthesis gas atmosphere₂Volume ratio with CO is 0.01:1 To 1000:1.

63. the purposes according to paragraph 59 or 60, wherein, the H in the synthesis gas₂Volume ratio with CO is 0.5:1 To 3.0:1st, preferably 1.0:1 to 2.5:1st, more preferably 1.2:1 to 2.2:1st, most preferably 1.5:1 to 2.0:1.

64. the purposes according to any one of paragraph 59-63, wherein, the Fischer-Tropsch synthesis with continous way or Formula of having a rest course of reaction is carried out.

65. the purposes according to any one of paragraph 59-64, wherein, the Fischer-Tropsch synthesis is with continuous reaction Process is carried out, and reaction velocity is 100~60000NL/Kg/h.

66. the purposes according to any one of paragraph 59-65, wherein, the Fischer-Tropsch synthesis uses one or many Platform fixed bed reactors, micro passage reaction, continuously stir slurry bed system tank reactor, jet-loop formula reactor, slurry drum Steep tower reactor or fluidized-bed reactor is carried out.

67. the purposes according to any one of paragraph 59-66, wherein, the pressure of the Fischer-Tropsch synthesis for 1.0~ 6.0MPa, temperature is 120~350 DEG C.

68. the purposes according to paragraph 59 or 60, wherein, the fischer-tropsch synthetic catalyst is Co catalysts, the conjunction Into the H in gas₂Volume ratio with CO is 1.0:1 to 3.0:1st, preferably 1.5:1 to 2.5:1st, most preferably 1.8:1 to 2.2:1.

69. the purposes according to paragraph 68, wherein, the pressure of the Fischer-Tropsch synthesis is 1.0~6.0MPa, preferably 1.5~4.5MPa, optimal 2.0~3.0MPa；Preferable temperature be 150~280 DEG C, preferably 180~260 DEG C, most preferably 200~ 240℃。

70. the purposes according to paragraph 68 or 69, wherein, the Fischer-Tropsch synthesis is entered with continuous reaction process OK, reaction velocity is 100~25000NL/Kg/h, preferably 1000~20000NL/Kg/h, optimal 5000~10000NL/Kg/h.

71. the purposes according to paragraph 59 or 60, wherein, the fischer-tropsch synthetic catalyst is iron catalyst, the conjunction Into the H in gas₂Volume ratio with CO is 0.5:1 to 3.0:1st, preferably 1.0:1 to 2.5:1st, more preferably 1.2:1 to 2.2:1st, it is optimal Select 1.5:1 to 2.0:1.

72. the purposes according to paragraph 71, wherein, the pressure of the Fischer-Tropsch synthesis is 1.0~6.0MPa, preferably 1.5~5.5MPa, more preferably 2.0~5.0MPa, most preferably 2.5~4.0MPa；Temperature be 220~350 DEG C, preferably 240~330 DEG C, most preferably 260~300 DEG C.

73. the purposes according to paragraph 71 or 72, wherein, the Fischer-Tropsch synthesis is entered with continuous reaction process OK, reaction velocity is 100~60000NL/Kg/h, preferably 1000~40000NL/Kg/h, most preferably 10000~20000NL/ Kg/h。

The invention is not restricted to preferred embodiment described herein and embodiment, and without departing from the mesh of the present invention , those skilled in the art can modify to these embodiments and application.

Embodiment

Embodiment 1

The hexagonal phase boron nitride carrier of high-specific surface area is prepared using ball-milling method：By the commercialized hexagonal phase boron nitride of 20g (purity 99.0%, 5 μm of particle diameter, specific surface area 21m²/ g, Qingzhou City circumference boron nitride factory), 200ml ethanol, 65ml zirconium oxide beads (0.5mm) is added in 500ml zirconium oxide abrasive tanks and sealed, and air in tank is replaced as into nitrogen, is ground under 300rpm rotating speeds 24h.Gained boron nitride powder is not washed with deionized, filtered, the dried overnight at 80 DEG C, then in 500 DEG C in Muffle furnace Lower roasting 5h, the hexagonal phase boron nitride (h-BN) of gained is labeled as Exam-1, its XRD spectrum as shown in figure 1, and texture property row In table 1.

Embodiment 2

Adopt and prepare boron nitride carrier with the following method：By 17.4g B₂O₃, 75.1g urea and 2.8g Fe₂O₃Grinding is uniform, It is fitted into 500ml stainless steel autoclaves and seals, autoclave is heated to 1000 DEG C with 10 DEG C/min heating rate and kept 5h is reacted, and the pressure of reaction is 9.5MPa.By the 3M hydrochloric acid solution diafiltrations of obtained sample powder, then with ethanol and go from Sub- water cyclic washing removes impurity element, then in an oven in 80 DEG C of dried overnights, finally with 5 DEG C/min's in Muffle furnace Heating rate is heated to 500 DEG C and is calcined 5h at such a temperature, and the BN carrier indiciums of gained are Exam-2, its XRD spectrum such as Fig. 2 It is shown, and texture property is listed in Table 1 below.

Embodiment 3

Nitridation silicon carrier (Si is prepared using ultrasonic method₃N₄)：By the commercialized silicon nitrides of 20g, (purity 99.0% compares surface Product 71m²/ g, the promise new high-tech material development corporation, Ltd. of Qinhuangdao one) and 400ml deionized waters be mixed into slurries, be put into In 1000ml ultrasound cups, ultrasonic (power is 150W) crushes 8h, is then washed with deionized, filters, in 110 DEG C of baking oven Dried overnight, is finally heated to 500 DEG C with 5 DEG C/min heating rate in Muffle furnace and is calcined 5h at such a temperature.Gained Silicon nitride carrier indicium be Exam-3, its XRD spectrum as shown in figure 3, and texture property be listed in Table 1 below.

Embodiment 4

Infusion process prepares the cobalt-base catalyst of boron nitride and silicon nitride load：Weigh 4.93g cabaltous nitrate hexahydrates (Co load Carrying capacity is 10wt%) it is dissolved in deionized water, according to 1:1 volume ratio is impregnated into 10g embodiment 1, the and of embodiment 2 respectively H-BN, BN and Si prepared by embodiment 3₃N₄On carrier, 8 hours are stood, in an oven in dried overnight at 110 DEG C, in Muffle furnace In be heated to 350 DEG C with 1 DEG C/min heating rate and be calcined 2 hours at such a temperature, what is obtained respectively urging in oxidation state The composition of agent is 10Co/100BN, 10Co/100BN and 10Co/100Si₃N₄, be respectively labeled as Exam-4a, Exam-4b and Exam-4c, its texture property, reduction degree and decentralization are listed in Table 1 below.

F- T synthesis performance test：0.5g above-mentioned each catalyst is taken respectively, and dilutes well mixed with 2ml carborundum, Internal diameter is placed in in 10mm, a length of 50mm of constant temperature zone fixed bed reactors.Catalyst is in H₂In at 375 DEG C reduce 6 hours, It is cooled to 160 DEG C.Then by 64%H₂/ 31%CO/5%Ar (volume ratio) synthesis gas is passed through in reactor, and pressure is 2.0MPa, temperature of reactor is improved to 220 DEG C by 0.1 DEG C/min heating rate, regulation reaction velocity is 5000NL/Kg/ H, keeps reaction more than 100 hours.Then reaction temperature is improved to 250 DEG C, regulation air speed is 12000NL/Kg/h, keeps this Conditioned response about 50 hours；Then 220 DEG C are cooled to again, regulation air speed is 5000NL/Kg/h, reaction is maintained more than 24 hours. During reaction use gas chromatographic analysis reactor tail gas composition, and for calculate reaction CO conversion ratios, selectivity of product and Stability.The results are shown in Table 2 for the Fischer-Tropsch synthesis of above-mentioned each catalyst.

Embodiment 5

Infusion process prepares 20Co1Mn0.1Ru/100BN catalyst：Weighing 9.88g cabaltous nitrate hexahydrates, (Co loading is 20wt%), 0.52g manganese nitrates (50wt%), 0.67g nitrosyl nitric acid ruthenium solution (concentration is 1.5wt%) are dissolved in deionization In water, according to 1:1 volume ratio be impregnated into 10g embodiment 2 preparation BN carriers on, stand 8 hours, in nitrogen atmosphere in 110 DEG C of dried overnights, are calcined to 350 DEG C and are kept for 2 hours with 1 DEG C/min heating rate in Muffle furnace, what is obtained is in The composition of the catalyst of oxidation state is 20Co1Mn0.1Ru/100BN, labeled as Exam-5, its texture property, reduction degree and scattered Degree is listed in Table 1 below.F- T synthesis performance test is carried out according to method same as Example 4, the results are shown in Table 2.

Embodiment 6

Using the Co catalysts of co-precipitation legal system boron nitride load：Weigh 24.71g cabaltous nitrate hexahydrates, 5.18g50% nitre Sour manganese solution, 0.01g platinum chlorides are dissolved in 100ml deionized waters, and the boron nitride that the preparation of 10g embodiments 2 is then weighed again is carried Body is mixed with above-mentioned solution, and uniform suspension is formed by the way of ultrasonic disperse.Under stirring into above-mentioned suspension Ammonia spirit to the pH value that 1mol/L is added dropwise is 8~9, forms precipitation.By precipitation filtering, washing, stayed overnight in atmosphere in 120 DEG C Dry, be heated to 450 DEG C with 1 DEG C/min heating rate in Muffle furnace and be calcined 5 hours at such a temperature, obtain being in oxygen The composition for changing state catalyst is 50Co10Mn0.06Pt/100BN, labeled as Exam-6, its texture property, reduction degree and decentralization It is listed in Table 1 below.

F- T synthesis performance test is carried out according to method same as Example 4, the results are shown in Table 2.

Embodiment 7

The cobalt-base catalyst of boron nitride load is prepared using infusion process：Except cabaltous nitrate hexahydrate consumption for 12.35g, Replace manganese nitrate with 0.72g Fe(NO3)39H2Os and replaced with 0.02g palladium nitrates outside nitrosyl nitric acid ruthenium, other material amounts Same as Example 5 with other operating conditions, the composition of the obtained catalyst in oxidation state is 25Co1Fe0.1Pd/ 100BN, labeled as Exam-7, its texture property, reduction degree and decentralization are listed in Table 1 below.

Embodiment 8

Infusion process prepares 10Co2Mn0.07Ir/100BN catalyst：Except replacing cobalt nitrate with 4.04g cobalt chlorides, using 0.47g manganese chlorides replace manganese nitrate and replaced with 0.01g iridium chlorides outside nitrosyl nitric acid ruthenium, other material amounts and other behaviour The composition for making the catalyst in oxidation state that condition is same as Example 5, obtains is 10Co2Mn0.07Ir/100BN, mark For Exam-8, its texture property, reduction degree and decentralization are listed in Table 1 below.

Embodiment 9

Using the Co catalysts of co-precipitation legal system boron nitride load, in addition to being adjusted to following parameter and condition, its Its material amounts and other operating conditions are same as Example 6, and the composition of the obtained catalyst in oxidation state is 100Co8Zn0.05Au/100BN, labeled as Exam-9, its texture property, reduction degree and decentralization are listed in Table 1 below：Use 40.37g Cobalt chloride hexahydrate replaces cobalt nitrate, replaces manganese nitrate with 1.66g zinc chloride, replaces nitrogen with the chlorogold solutions of 0.015g 50% Change platinum, dissolve them in 500ml deionized waters.

Embodiment 10

The Co catalysts of boron nitride load are prepared using coprecipitation, in addition to being adjusted to following parameter and condition, Other material amounts and other operating conditions are same as Example 6, and the composition of the resulting catalyst in oxidation state is 200Co25Zn0.04Rh/100BN, catalyst is labeled as Exam-10, and its texture property, reduction degree and decentralization are listed in Table 1 below： Replace cobalt nitrate with 80.75g cobalt chloride hexahydrates, replace manganese nitrate with 5.20g zinc chloride, replace chlorination with 0.01g radium chlorides Platinum, is dissolved them in 500ml deionized waters.

Embodiment 11

In addition to replacing cobalt nitrate with 7.23g ferric nitrates, other material amounts and other operating conditions and the phase of embodiment 4 Together, the composition of the catalyst in oxidation state obtained is 10Fe/100BN, 10Fe/100BN and 10Fe/100BN, is marked respectively For Exam-11a, Exam-11b and Exam-11c, its texture property, reduction degree and decentralization are listed in Table 1 below.These three catalyst XRD spectrum as shown in Figure 4, Figure 5 and Figure 6, active metal exists with the iron oxide structure of high degree of dispersion, its crystallite dimension between 2-9nm。

F- T synthesis performance test：0.5g above-mentioned each catalyst is taken respectively, and dilutes well mixed with 2ml carborundum, Internal diameter is placed in in 10mm, a length of 50mm of constant temperature zone fixed bed reactors.Catalyst is in 98%H₂In/2%CO synthesis gas In reductase 12 4 hours at 320 DEG C, 220 DEG C are cooled to.Then by 63%H₂/ 37%CO synthesis gas is passed through in reactor, pressure For 2.0MPa, temperature of reactor is improved to 280 DEG C by 0.1 DEG C/min heating rate, regulation reaction velocity is 15000NL/ Kg/h, keeps reaction more than 100 hours.Then reaction temperature is improved to 300 DEG C, regulation air speed is 36000NL/Kg/h, is protected Hold this conditioned response about 50 hours；Then 280 DEG C are cooled to again, regulation air speed is 15000NL/Kg/h, reaction is maintained 24 hours More than.The composition of gas chromatographic analysis reactor tail gas is used during reaction, and for calculating CO conversion ratios, the product selection of reaction Property and stability.The results are shown in Table 2 for Fischer-Tropsch synthesis.

Embodiment 12

Except replacing the consumption increase of cobalt nitrate, manganese nitrate to be 1.31g, use 0.29g nitre with 14.47g Fe(NO3)39H2Os Sour copper substitution nitrosyl nitric acid ruthenium is simultaneously added outside 0.37g sodium nitrate, other material amounts and other operating conditions and embodiment 5 Identical, the composition of the obtained catalyst in oxidation state is 20Fe2.5Mn0.2Cu1Na/100BN, labeled as Exam-12, its Texture property, reduction degree and decentralization are listed in Table 1 below.

F- T synthesis performance test is carried out according to the identical method of embodiment 11, the results are shown in Table 2.

Embodiment 13

In addition to being carried out as follows adjustment, other material amounts and other operating conditions are identical with embodiment 12, obtain The composition of catalyst in oxidation state is 30Fe1Mo0.06Pt0.5K/100BN, labeled as Exam-13, its texture property, also Former degree and decentralization are listed in Table 1 below：Taken with 14.52g ferric chloride hexahydrates substitution Fe(NO3)39H2O, with 0.18g ammonium heptamolybdates Replace copper nitrate for manganese nitrate, with 0.01g platinum chlorides, replace sodium nitrate with 0.10g potassium chloride；Using step impregnation method first by seven Ammonium molybdate is carried on the boron nitride carrier of the preparation of embodiment 2, then above-mentioned other metal salts is supported on carrier.

Embodiment 14

The ferrum-based catalyst of boron nitride load is prepared using coprecipitation, except being adjusted to following parameter and condition Outside, other material amounts and other operating conditions are same as Example 9, and the composition of the resulting catalyst in oxidation state is 100Fe5Cr0.1Pd5Mg/100BN, labeled as Exam-14, its texture property, reduction degree and decentralization are listed in Table 1 below：With 72.35g Fe(NO3)39H2Os replace cobalt chloride hexahydrate, replace zinc chloride with 3.85g chromic nitrates, are replaced with 0.02g palladium nitrates Chlorauride, adds 3.05g magnesium nitrates, dissolves them in 500ml deionized waters.

Embodiment 15

The ferrum-based catalyst of boron nitride load is prepared using coprecipitation, except being adjusted to following parameter and condition Outside, other material amounts and other operating conditions are same as Example 9, and the composition of the obtained catalyst in oxidation state is 200Fe8Zr0.07Ir5Ca/100BN, labeled as Exam-15, its texture property, reduction degree and decentralization are listed in Table 1 below：With 96.81g ferric chloride hexahydrates replace cobalt chloride hexahydrate, replace zinc chloride with 2.84g zirconyl chlorides, are taken with 0.01g iridium chlorides For chlorauride, 2.75g calcium chloride is added, is dissolved them in 500ml deionized waters.

Embodiment 16

The ferrum-based catalyst of boron nitride load is prepared using coprecipitation, except being adjusted to following parameter and condition Outside, other material amounts and other operating conditions are same as Example 9, and the composition of the resulting catalyst in oxidation state is 300Fe40Mn15Cu5Sr/100BN, catalyst is labeled as Exam-16, and its texture property, reduction degree and decentralization are listed in table 1 In：Replace cobalt chloride hexahydrate with 217.0g Fe(NO3)39H2Os, replace zinc chloride with 20.9g manganese nitrates, use 13.43g nitric acid Copper replaces chlorauride, adds 2.40g plus strontium chloride, dissolves them in 500ml deionized waters；Then 10g embodiments 2 are weighed again The boron nitride carrier of preparation is mixed with above-mentioned solution, and uniform suspension is formed by the way of ultrasonic disperse；Under stirring Ammonia spirit to the pH value that 1mol/L is added dropwise into above-mentioned suspension is 8~9, forms precipitation；By precipitation filtering, washing, 120 DEG C dried overnight, is heated to 450 DEG C with 1 DEG C/min heating rate in Muffle furnace and is calcined 5 hours at such a temperature.According to F- T synthesis performance test is carried out with the identical method of embodiment 11, the results are shown in Table 2.

Comparative example 1

Except with business silicon nitride (the promise new high-tech material development corporation, Ltd. of Qinhuangdao one, purity>99.0%, specific surface area 70m²/ g) replace embodiment 1, h-BN, BN of embodiment 2 and the preparation of embodiment 3 and nitrogenize outside silicon carrier, other material amounts Identical with embodiment 4 with other operating conditions, the composition of the obtained catalyst in oxidation state is 10Co/100Si₃N₄, CE-4 is designated as, its texture property, reduction degree and decentralization are listed in Table 1 below.Fischer-Tropsch conjunction is carried out according to method same as Example 4 Into performance test, the results are shown in Table 2.

Comparative example 2

Except with business boron nitride, (Qingzhou City has an area of boron nitride factory, purity >=99.0%, specific surface area 21m²/ g) substitution Outside h-BN, BN and nitridation silicon carrier prepared by embodiment 1, embodiment 2 and embodiment 3, other material amounts and other operations Condition is identical with embodiment 11, and the composition of the obtained catalyst in oxidation state is 10Fe/100BN, is designated as CE-3, its Texture property, reduction degree and decentralization are listed in Table 1 below.F- T synthesis performance survey is carried out according to the identical method of embodiment 11 Examination, the results are shown in Table 2.

Comparative example 3

Except being prepared with 13.3g boehmites (Shandong Aluminum Plant produces, the aluminum oxide 75wt% containing butt) substitution embodiment 2 Boron nitride carrier outside, other material amounts and other operating conditions are identical with embodiment 6, obtain be in oxidation state Catalyst composition be 25Co5Mn0.06Pt/100Al₂O₃, CE-1 is designated as, its texture property, reduction degree and decentralization are listed in In table 1.F- T synthesis performance test is carried out according to method same as Example 4, the results are shown in Table 2.

Comparative example 4

Except with 10.0g white carbons (Shanghai jump river titanium white heavy chemicals Co., Ltd, purity >=99.8%, specific surface area 300m²/ g) replace outside boron nitride carrier prepared by embodiment 2, other material amounts and other operating conditions and embodiment 13 Identical, the composition of the obtained catalyst in oxidation state is 30Fe1Mo0.06Pt0.5K/100SiO₂, CE-2 is designated as, Its texture property, reduction degree and decentralization are listed in Table 1 below.F- T synthesis performance survey is carried out according to the identical method of embodiment 11 Examination, the results are shown in Table 2.

Comparative example 5

According to document RSC Advances, 2016,6, the 38356-38364 pages disclosed method is prepared for F- T synthesis The iron catalyst of the hexagonal phase boron nitride load of reaction, the composition of obtained catalyst is 33Fe/100BN, is designated as CE-5, it is knitted Structure property, reduction degree and decentralization are listed in Table 1 below.F- T synthesis performance test is carried out according to the identical method of embodiment 11, The results are shown in Table 2.

Each carrier and the texture property of catalyst that are prepared in the embodiment 1-16 of table 1 and comparative example 1-5, reduction degree and Decentralization

- represent not test relevant item

The catalyst prepared in the embodiment 1-16 of table 2 and comparative example 1-5 Fischer-Tropsch synthesis activity, selectivity and Stability

As shown in table 2, the Co catalysts of the boron nitride of the present invention containing high-specific surface area and/or nitridation silicon carrier Show very high F- T synthesis catalytic activity and excellent C₅ ⁺Hydrocarbon-selective, in the experience long-time and 250 of more than 200 hours After high temperature harshness reaction more than DEG C, the activity of most of catalyst remains to return to more than the 80% of initial activity, shows The catalyst of the present invention has good stability.Particularly embodiment 6 and embodiment 8 catalyst (Exam-6 catalyst and Exam-8 catalyst) show optimal F- T synthesis catalytic performance.By comparison, the nitrogen containing commercialized low specific surface area SiClx or Al₂O₃The activity and stability of CE-1 the and CE-3 catalyst of carrier, which are then far below, has the active phase composition of similar metals Exam-4c and Exam-6 catalyst.

Similarly, the iron catalysis of the boron nitride containing high-specific surface area and/or nitridation silicon carrier that are prepared in the present invention Agent shows higher F- T synthesis catalytic activity and same excellent C under higher reaction temperature₅ ⁺Hydrocarbon selective. Undergo after long period and pyroreaction, the activity of the iron catalyst of these nitride load can return to the 70% of initial activity More than, illustrating the catalyst of the present invention has excellent stability and catalytic activity.Particularly Exam-13 catalyst, its final state Fischer-Tropsch synthesis performance and initial reaction performance are very nearly the same.By comparison, the nitridation containing commercialized low specific surface area Boron or SiO₂The activity of the CE-2 and CE-4 catalyst of carrier is poor with stability.In addition, being urged with the CE-5 of comparative example 5 As can be seen that the metal grain size (2-9nm) for the catalyst that the present invention is prepared is remote small after the result of agent is compared The metallic iron of the catalyst prepared in document report (RSC Advances, 2016,6, the 38356-38364 pages) it is flat Equal size (25-40nm), while the decentralization (15-70%) of the active metal in the catalyst of the present invention is also far longer than document The decentralization (3-5%) of the active metal of the catalyst of report.Thus, (the 10-40 under the air speed level far above document report Times), CO conversion ratio of the catalyst of the present invention in Fischer-Tropsch synthesis still is able to suitable with document report, i.e. this hair Bright catalyst has higher 10-40 times of catalytic activity, and urging using the present invention compared with the catalyst in above-mentioned document The byproduct methane and CO for the Fischer-Tropsch synthesis that agent is carried out₂Selectivity is lower.

It can thus be seen that the catalysis of the boron nitride disclosed by the invention containing high-specific surface area and/or nitridation silicon carrier Agent can realize very excellent Fischer-Tropsch synthesis performance.

Claims

1. a kind of fischer-tropsch synthetic catalyst, wherein, the catalyst is included：Active component, the active component is selected from the At least one of Group VIIIB；Optional promoter metal；And nitride carrier, the carrier is specific surface area Not less than 80m²/ g boron nitride, silicon nitride or its mixture；

2. catalyst according to claim 1, wherein, the decentralization of the active component is 15%-75%.

3. catalyst according to claim 1 or 2, wherein, the active component be in iron, cobalt, nickel and ruthenium extremely Few one kind.

4. the catalyst according to any one of claim 1-3, wherein, the boron nitride is hexagonal phase boron nitride.

5. the catalyst according to any one of claim 1-4, wherein, the silicon nitride be tripartite's phase silicon nitride and/or Hexagonal phase silicon nitride.

6. the catalyst according to any one of claim 1-5, wherein, the active metal:Auxiliary agent:The mass ratio of carrier For (0.1~300):(0.002~30):100.

7. the method for the fischer-tropsch synthetic catalyst any one of claim 1-6 is prepared, wherein, methods described includes as follows Step：(1) prepare specific surface area and be not less than 80m²/ g nitride carrier；(2) using before the active metal as active component The presoma for driving body and optional promoter metal is carried on the nitride carrier, forms catalyst precursor；(3) will be described Complex catalyst precursor is body formed, the catalyst precursor after being molded；(4) catalyst precursor after the shaping is done Dry and roasting, obtains the catalyst.

8. method according to claim 7, in step (1), institute is prepared by mechanical means or heat chemistry synthetic method State nitride carrier.

9. the fischer-tropsch synthetic catalyst any one of claim 1-6 is used to catalyze and synthesize gas in Fischer-Tropsch synthesis Prepare the purposes of hydrocarbon compound.

10. purposes according to claim 9, wherein, before the catalyst is applied to Fischer-Tropsch synthesis, in advance The catalyst is set to be reduced in reducing atmosphere.